Porosity Of Films Research Articles

How to process P(VDF-TrFE) thin films for controlling short circuits in flexible non-volatile memories

Severe electrical shorting is one of the biggest challenges for the development of flexible non-volatile ferroelectric memories with low operation voltage. In this work, short circuits in flexible ferroelectric capacitors based on copolymer poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)], were explicitly investigated. It was found that processing conditions of P(VDF-TrFE) films have huge effects on electrical shorting conditions. Both deciding factors such as drying temperatures, solvent evaporation rates, and solution concentrations, and plausible factors such as post-drying thermal annealing, were clearly identified. These deciding factors were found to affect short circuits by altering the film porosity, surface roughness, and defect conditions in P(VDF-TrFE) thin films. The detailed correlation of these factors with film porosity were established and explained within the framework of liquid-liquid phase separation. The correlation with the surface roughness and defect conditions were explained with Marangoni convection. The net effects of these factors on electrical shorting conditions are rather complicated because a favorable factor with regards to film porosity may be detrimental in terms of surface roughness and/or defects. So these factors have to been carefully tailored to control short circuits and generate high yields in P(VDF-TrFE) thin film memory devices. Comparative study shows that drying at 80 °C in open air is the optimal condition for processing P(VDF-TrFE) thin films from PGMEA solution. Under this optimal drying condition, a yield of 76% was achieved from large-area devices of about 200 μm × 200 μm with thin P(VDF-TrFE) films of about 200 nm processed with roll-2-roll compatible techniques on plastic substrates. An effective two-step approach to manufacturing P(VDF-TrFE) layers for ferroelectric capacitors with low operation voltage but high yields, is presented. The key information gained from this work on ferroelectric capacitors could be generalized to another type of ferroelectric memories, namely ferroelectric field effect transistors. So it provides researchers and engineers a general guideline on how to control short circuits by processing P(VDF-TrFE) thin films for flexible non-volatile memories.

<i>In Situ</i> Growth of Hydrophobic ZIF-8 on Poly(Aryl Ether Nitrile) as Low Dielectric Film

Flexible polymers with excellent low dielectric constant stability are promising for application in the field of high-speed communications. In this work, a series of surface-modified ZIF-8 on polyarylene ether nitrile (PEN) as low dielectric films are prepared by phase inversion method. The experimental results show that by changing the content of Zn2+, the surface roughness, hydrophobicity, pore size, dielectric properties and mechanical properties of porous PEN films can be effectively adjusted. The surface roughness of porous PEN films effectively increases from 47.9 nm to 72.5 nm as the content of ZIF-8 grown in situ on porous PEN films surface increases. The static water contact angle of porous PEN films surface increases from 115° to 152°. The porosity of porous PEN films increases from 73.7% to 75.8% as the pore size of the fracture surface increases, and the dielectric constant decreases from 1.85 to 1.68 accordingly. Furthermore, the porous PEN films exhibit outstanding mechan ical flexibility, and the elongation at break of porous PEN films is as high as 89.6%. In-situ growth of ZIF-8 on PEN as low dielectric film expands the application of PEN in the field of high-speed communication.

Planar Microsupercapacitors Based on Oblique Angle Deposited Highly Porous TiN Thin Films.

Microsupercapacitors are gaining increasing interest for energy storage in miniaturized electronic devices. However, the production of porous electrode material with standard microfabrication techniques is a big problem. Here, we report on the oblique angle deposition of highly porous and nanostructured columnar titanium nitride (TiN) films on silicon substrate using magnetron sputtering for high-performance microsupercapacitors. The intercolumnar porosity of the sputtered TiN films can be systematically controlled as a function of the oblique angle α achieved by tilting the substrate. The denser morphologies in TiN films deposited at α = 0° lead to moderate capacitive behavior in a 1 M Na2SO4 electrolyte solution. Meanwhile, a high areal capacitance of 17.5 mF·cm-2 is obtained for a 60° oblique angle due to high intercolumnar porosity in films, which increases the specific surface area and facilitates easy electrolyte permeation. The electrodes also retain 88.2% of the initial specific capacitance after 10,000 charging/discharging cycles. A planar interdigitated microsupercapacitor has been subsequently fabricated based on an optimized TiN thin film serving as both an efficient electrode and a current collector. TThe device was electrochemically tested using polyvinyl alcohol (PVA)-Na2SO4 hydrogel electrolyte allowing a voltage window of 1.8 V and showed energy densities of 0.46 μWh·cm-2 while maintaining a high-power density of 703.12 μWh·cm-2. This work gives insight into the use of oblique angle deposition for obtaining highly porous films of other electrode materials for microsupercapacitor applications with the advantage of using a simple microfabrication process.

Dispersing Agents Impact Performance of Protonated Phosphonic Acid High-Temperature Polymer Electrolyte Membrane Fuel Cells

The microstructure of ionomers plays a significant role in the performance of high-temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). Here, we establish direct correlations between the properties of dispersing agents and the microstructure of a protonated phosphonic acid ionomer. Most importantly, the formation of the porous structure of a protonated phosphonic acid ionomer depends on the pKa of the liquid media. Namely, the acid–base interaction between the charged polymer and dispersing agents determines the porosity in the ionomer thin films. The HT-PEMFC performance increases with the level of porosity of the ionomer, as the pores enable fast reactant gas accessibility. This study concludes the importance of the pKa of ionomers’ dispersing media for the HT-PEMFC performance.

Preparation and characterization of graphene oxide-Chitosan composite film for ultrathin hyaluronic acid hydrogels

ABSTRACT Mechanical properties of hyaluronic acid (HA) hydrogels are too poor to be prepared as an ultra-thin hydrogels, so to provide a supporting skeleton for them is important. Herein, the porous film based on chitosan(CS)、PEG-20000 and graphene oxide (GO) were prepared for ultra-thin hydrogels. CS is a suitable polymer to prepare films. The added PEG-20000 endowed the film porosity. And the addition of GO improved the mechanical of the film. When CS:PEG = 3:2 and the GO solution proportion was 15%, the porous film exhibited the best comprehensive properties, with a tensile strength of 5.593 MPa, an elongation at break of 45.833%, a water permeation of 1.4099 g at 12 h, a porosity of 62.3% and an average pore size of 1.88 um. Blood compatibility experiments and cell experiments have proved that the film hydrogel has strong biocompatibility, indicating it can be a promising biomaterial.

Wafer-Scale Fabrication and Transfer of Porous Silicon Films as Flexible Nanomaterials for Sensing Application.

Flexible sensors are highly advantageous for integration in portable and wearable devices. In this work, we propose and validate a simple strategy to achieve whole wafer-size flexible SERS substrate via a one-step metal-assisted chemical etching (MACE). A pre-patterning Si wafer allows for PSi structures to form in tens of microns areas, and thus enables easy detachment of PSi film pieces from bulk Si substrates. The morphology, porosity, and pore size of PS films can be precisely controlled by varying the etchant concentration, which shows obvious effects on film integrity and wettability. The cracks and self-peeling of Psi films can be achieved by the drying conditions after MACE, enabling transfer of Psi films from Si wafer to any substrates, while maintaining their original properties and vertical alignment. After coating with a thin layer of silver (Ag), the rigid and flexible PSi films before and after transfer both show obvious surface-enhanced Raman scattering (SERS) effect. Moreover, flexible PSi films SERS substrates have been demonstrated with high sensitivity (down to 2.6 × 10−9 g/cm2) for detection of methyl parathion (MPT) residues on a curved apple surface. Such a method provides us with quick and high throughput fabrication of nanostructured materials for sensing, catalysis, and electro-optical applications.

Ellipsometry‐Based Approach for the Characterization of Mesoporous Thin Films for H2 Technologies

Porous thin layer materials are gaining importance in different fields of technology and pose a challenge to the accurate determination of materials’ properties important for their function. Herein, a hybrid measurement technique using ellipsometry together with other independent methods for validation, is demonstrated. Ellipsometry provides information about the porosity of different mesoporous films (PtRuNP/OMC = 45%; IrOx = 46%) as well as about the pore size (pore radius of ≈5 nm for PtRuNP/OMC). In addition, the electronic structure of a material, such as intraband transitions of a mesoporous IrOx film, can be identified, which can be used to better understand the mechanisms of chemical processes. In addition, it is shown that ellipsometry can be used as a scalable imaging and visualization method for quality assurance in production. These require accurate and traceable measurements, with reference materials playing an important role that include porosity and other related properties. It is shown that novel analytical methods are useful for improving analytical work in this entire field.

Controlled Porosity in Ferroelectric BaTiO3 Photoanodes.

The use of ferroelectric polarization to promote electron–hole separation has emerged as a promising strategy to improve photocatalytic activity. Although ferroelectric thin films with planar geometry have been largely studied, nanostructured and porous ferroelectric thin films have not been commonly used in photo-electrocatalysis. The inclusion of porosity in ferroelectric thin films would enhance the surface area and reactivity, leading to a potential improvement of the photoelectrochemical (PEC) performance. Herein, the preparation of porous barium titanate (pBTO) thin films by a soft template-assisted sol–gel method is reported, and the control of porosity using different organic/inorganic ratios is verified by the combination of scanning electron microscopy and ellipsometry techniques. Using piezoresponse force microscopy, the switching of ferroelectric domains in pBTO thin films is observed, confirming that the ferroelectric polarization is still retained in the porous structures. In addition, the presence of porosity in pBTO thin films leads to a clear improvement of the PEC response. By electrochemical poling, we also demonstrated the tuning of the PEC performance of pBTO thin films via ferroelectric polarization. Our work offers a simple and low-cost approach to control the morphology optimization of ferroelectric thin films, which could open up the development of materials with great potential for PEC applications.

Deposition, microstructure, performance of diamond-like carbon film with Ni/Cu interlayer

Diamond-like carbon (DLC) films containing single copper (Cu), single nickel (Ni) and double nickel/copper interlayers were fabricated on LY-12 aluminum (Al) alloy by electrodeposition. The influence of different interlayers on the microstructure, microhardness, friction and wear properties and electrochemical behavior of the films was investigated. The morphological results show that the porosity of DLC films was reduced and the particles were refined after the introduction of a double interlayer. Raman and X-ray photoelectron spectroscopy results confirm that the amorphous characteristics of DLC films containing nickel and copper interlayers were enhanced, and the content of sp3 carbon in the films was increased. Besides, an optimal microhardness of 210.67 HV was achieved due to the high sp3 carbon content of the double nickel/copper–DLC film. Meanwhile, the nickel/copper–DLC film possessed excellent wear resistance, which benefits from the synergistic effect of the copper and nickel interlayer. Nickel as the supporting layer and copper as the lubricating layer alleviated the wear and friction of the film. Simultaneously, the deposition of a double interlayer increased the density of the film, which further prevented the invasion of corrosion ions, so the film had superior electrochemical properties.

Effect of porosity on thickness uniformity of MgF2 films on spherical substrates.

Simulation based on Knudsen's law shows that film thickness uniformity above 99% can be realized on spherical substrates with optimized profiles of shadowing masks. However, a type of optical thickness nonuniformity is revealed when the masks are applied for thickness correction of MgF2 films experimentally. The optical thickness nonuniformity depends on steepness of the spherical surfaces and reaches 5% approximately for surfaces with CA/RoC = 1.22. Porosity of the MgF2 film is superimposed on Knudsen's law to interpret the optical thickness nonuniformity. For theoretical simulation, the influence of porosity on optical thickness distribution is characterized by a new parameter that describes nonlinear dependence of deposition rate on cosine function of molecular injection angles in Knudsen's law. Utilizing the optimized deposition model, optical thickness uniformity of MgF2 films approaching to or above 99% has been achieved for surfaces of different steepness in a single coating run.

Etching time effect on morphological, optical and photoelectrochemical properties of BiVO4 electrodeposited films

The impact of etching time on the surface morphology, crystallinity, light absorption, and the photoelectrochemical characteristics of BiVO4 thin films prepared by electrodeposition method has been studied to remove excess V2O5 on top of BiVO4. BiVO4 films were first electrodeposited on fluorine-doped tin oxide (FTO) electrodes at a deposition time of 30 min, followed by annealing at 500 °C. Excess V2O5 was then removed by chemical etching in an aqueous KOH solution. The samples were characterized by FE-SEM, XRD, EDX, EDX-mapping, UV–Vis, and photoelectrochemical analyses. The morphology, porosity, crystallinity, and light absorption of BiVO4 films and those treated with KOH for 20 min (the optimal etching time, which yielded the highest photocurrent) could be changed by etching time, according to the results. The photocurrent density of the BiVO4 film etched for 20 min was 60 µA/cm2 at +1.0 V vs. Ag/AgCl which was 8.2 times higher than the corresponding value for BiVO4 film prior to etching. The very long duration (30 mins) led to the poor performance of the films prepared since only 22 µA/cm2 at +1.0 V vs. Ag/AgCl of photocurrent was generated. Thus, the etching time must be well optimized to ascertain the complete removal of the excess V2O5 without damaging the BiVO4 film.

Investigating the variation in the optical properties of TiO2 thin-film utilized in bifacial solar cells using machine learning algorithm

Among various solar cell architectures, dye-sensitized solar cells (DSSCs) and perovskite solar cells have demonstrated the capability of being bifacial as both can be fabricated on conducting glass electrodes. In both cells, TiO2 plays a key role in the optoelectronic properties of the cell. Various studies have reported a range of recipes and deposition techniques for TiO2 thin films. Such variety introduces some uncertainties into the optical properties of the prepared films as well as in the process repeatability. Here, we utilized machine learning methods to correlate the film porosity to the film refractive index, making it capable of studying the impact of varying the fabrication and deposition techniques. Image postprocessing for scanning electron microscope measurements was utilized to estimate the film porosity, and the refractive index was calculated from the T–λ spectra. Four sets of samples with complete bifacial DSSCs were fabricated and characterized. They recorded a maximum current of 23.42 mA. They were fabricated using carboxymethyl cellulose-based suspension and deposited via the spin-coating sol-gel method. The fabricated cells showed an overall conversion efficiency of 7.9% under optical injection of the AM1.5G spectrum from the front side and LED indoor lighting from the counter electrode.

Respiratory Monitoring by Ultrafast Humidity Sensors with Nanomaterials: A Review.

Respiratory monitoring is a fundamental method to understand the physiological and psychological relationships between respiration and the human body. In this review, we overview recent developments on ultrafast humidity sensors with functional nanomaterials for monitoring human respiration. Key advances in design and materials have resulted in humidity sensors with response and recovery times reaching 8 ms. In addition, these sensors are particularly beneficial for respiratory monitoring by being portable and noninvasive. We systematically classify the reported sensors according to four types of output signals: impedance, light, frequency, and voltage. Design strategies for preparing ultrafast humidity sensors using nanomaterials are discussed with regard to physical parameters such as the nanomaterial film thickness, porosity, and hydrophilicity. We also summarize other applications that require ultrafast humidity sensors for physiological studies. This review provides key guidelines and directions for preparing and applying such sensors in practical applications.

Nanostructured Ge and GeSn films by high-pressure He plasma sputtering for high-capacity Li ion battery anodes

We fabricated nanostructured Ge and GeSn films using He radio-frequency magnetron plasma sputtering deposition. Monodisperse amorphous Ge and GeSn nanoparticles of 30–40 nm size were arranged without aggregation by off-axis sputtering deposition in the high He-gas-pressure range of 0.1 Torr. The Ge film porosity was over 30%. We tested the charge/discharge cycle performance of Li-ion batteries with nanostructured Ge and GeSn anodes. The Ge anode with a dispersed arrangement of nanoparticles showed a Li-storage capacity of 565 mAh/g after the 60th cycle. The capacity retention was markedly improved by the addition of 3 at% Sn in Ge anode. The GeSn anode (3 at% Sn) achieved a higher capacity of 1128 mAh/g after 60 cycles with 92% capacity retention. Precise control of the nano-morphology and electrical characteristics by a single step procedure using low temperature plasma is effective for stable cycling of high-capacity Ge anodes.

New bio-based polyester with excellent spinning performance: poly(tetrahydrofuran dimethanol-co-ethylene terephthalate).

With the excessive consumption of fossil energy, technologies that transform bio-based resources into materials have received more and more attention from researchers in recent decades. In this paper, a series of poly(ethylene 2,5-tetrahydrofuran dimethyl terephthalate; PEFTs) with different components were synthesized from 2,5-tetrahydrofuran dimethanol (THFDM), terephthalic acid (TPA), and ethylene glycol (EG). Their chemical structures and compositions were determined by FTIR, 1H NMR, and 13C NMR. With the increase in THFDM content, the crystallization, T m, and tensile strength of PEFTs gradually decrease because the introduced THFDM breaks the order of molecular chains, while the thermal stability and T g remain stable. PEFTs seem to present a significant shear thinning phenomenon, which was indicated by the rheological test. Electrospinning technology was used to explore the spinnability of PEFT; it was found that PEFTs have better spinning performance than PET. In addition, due to the good hydrophobicity and porosity of PEFT nanofiber films, they have potential application value in the manufacture of hydrophobic nanofiber and filter films.

Production and Properties of Microbial Polyhydroxyalkanoates Synthesized from Hydrolysates of Jerusalem Artichoke Tubers and Vegetative Biomass.

One of the major challenges in PHA biotechnology is optimization of biotechnological processes of the entire synthesis, mainly by using new inexpensive carbon substrates. A promising substrate for PHA synthesis may be the sugars extracted from the Jerusalem artichoke. In the present study, hydrolysates of Jerusalem artichoke (JA) tubers and vegetative biomass were produced and used as carbon substrate for PHA synthesis. The hydrolysis procedure (the combination of aqueous extraction and acid hydrolysis, process temperature and duration) influenced the content of reducing substances (RS), monosaccharide contents, and the fructose/glucose ratio. All types of hydrolysates tested as substrates for cultivation of three strains—C. necator B-10646 and R. eutropha B 5786 and B 8562—were suitable for PHA synthesis, producing different biomass concentrations and polymer contents. The most productive process, conducted in 12-L fermenters, was achieved on hydrolysates of JA tubers (X = 66.9 g/L, 82% PHA) and vegetative biomass (55.1 g/L and 62% PHA) produced by aqueous extraction of sugars at 80 °C followed by acid hydrolysis at 60 °C, using the most productive strain, C. necator B-10646. The effects of JA hydrolysates on physicochemical properties of PHAs were studied for the first time. P(3HB) specimens synthesized from the JA hydrolysates, regardless of the source (tubers or vegetative biomass), hydrolysis conditions, and PHA producing strain employed, exhibited the 100–120 °C difference between the Tmelt and Tdegr, prevailing of the crystalline phase over the amorphous one (Cx between 69 and 75%), and variations in weight average molecular weight (409–480) kDa. Supplementation of the culture medium of C. necator B-10646 grown on JA hydrolysates with potassium valerate and ε-caprolactone resulted in the synthesis of P(3HB-co-3HV) and P(3HB-co-4HB) copolymers that had decreased degrees of crystallinity and molecular weights, which influenced the porosity and surface roughness of polymer films prepared from them. The study shows that JA hydrolysates used as carbon source enabled productive synthesis of PHAs, comparable to synthesis from pure sugars. The next step is to scale up PHA synthesis from JA hydrolysates and conduct the feasibility study. The present study contributes to the solution of the critical problem of PHA biotechnology—finding widely available and inexpensive substrates.

ФОРМУВАННЯ ТА ХАРАКТЕРИЗАЦІЯ ПОРИСТОГО АНОДОВАНОГО ОКСИДУ АЛЮМІНІЮ, СИНТЕЗОВАНОГО ЕЛЕКТРОХІМІЧНО У ПРИСУТНОСТІ ОКИСЛЕНОГО ГРАФЕНУ

Purpose of the research: studying the effect of addition of carbon nanosized modifier graphene oxide on the formation of a porous film during the electrochemical oxidation of aluminum.Methods: UV-VIS spectra of graphene oxide suspension were obtained using a spectrophotometer, the thermogravimetric characteristics of anodized alumina were determined using a thermal analyzer, the surface characteristics were determined by the low-temperature nitrogen sorption-desorption method, the surface was calculated by the BET method, the morphology and ultrastructure of the surface were determined using electron microscope.Results: the possibility of using carbon materials for the electrochemical oxidation of aluminum was shown. The obtained electron micrographs indicate the effect of the inserted carbon modifier (graphene oxide) on the morphology of resulting oxide. As a result of this process we observe the formation of the cellular surface of the aluminium oxide with smaller pores compared with sample after synthesis without the modifier.It was shown that the addition of graphene oxide (0.25%) in the oxalic acid (0,3М) electrolyte effects on the stability of the anodizing process, the specific surface area of the sample of anodized aluminum synthesized with graphene oxide is determined as 35.5 m3/g, and it is three times higher than sample without modifier. According to sorption studies, it could be noted that the presence of nanosized graphene oxide in oxalic acid electrolyte leads to the formation of honey-comb pores with a smaller radius (22 nm), while the total volume of micropores increases. The obtained results allow us to conclude that graphene oxide as modifier is promising material for the preparation of anodized aluminum oxide matrices. In the future, these matrices could be used in processes of solutions and gases separation.Conclusions: The addition of graphene oxide into the electrolyte changes structure of porous anodized aluminum oxide and has shown the possibility of controlling the porosity of films.

Morphological control of nanostructured Ge films in high Ar-gas-pressure plasma sputtering process for Li ion batteries

We present a study on morphological control of nanostructured Ge films by the Ar gas pressure in plasma sputtering deposition. In the low Ar-gas-pressure range, aggregated islands of amorphous grains are formed on the film surface, while in the high-pressure range of 500 mTorr monodisperse nano-grains of about 30 nm in size are orderly arranged without aggregation. The film porosity shows a high value of over 10%. We tested the charge/discharge cycle performance of Li-ion batteries with nanostructured Ge films as anodes. The battery cell with an ordered arrangement structure maintained a high capacity of 434 mAh g−1 after 40 charge/discharge cycles, while that with an aggregated structure exhibited a rapid degradation of capacity to 5.08–183 mAh g−1. An ordered arrangement of Ge nano-grains with a high porosity, which is realized in a simple one-step procedure using high Ar-gas-pressure plasma sputtering, is effective for the stable cycling of high-capacity metal anodes.

Subtractive Low-Temperature Preparation Route for Porous SiO2 Used for the Catalyst-Assisted Growth of ZnO Field Emitters.

The possibility to gradually increase the porosity of thin films facilitates a variety of applications, such as anti-reflective coatings, diffusion membranes, and the herein investigated tailored nanostructuring of a substrate for subsequent self-assembly processes. A low-temperature (<160 °C) preparation route for porous silicon oxide (porSiO2) thin films with porosities of about 60% and effective refractive indices down to 1.20 is tailored for bulk as well as free-standing membranes. Subsequently, both substrate types are successfully employed for the catalyst-assisted growth of nanowire-like zinc oxide (ZnO) field emitters by metal organic chemical vapor deposition. ZnO nanowires can be grown with a large aspect ratio and exhibit a good thermal and chemical stability, which makes them excellent candidates for field emitter arrays. We present a method that allows for the direct synthesis of nanowire-like ZnO field emitters on free-standing membranes using a porSiO2 template. Besides the application of porSiO2 for the catalyst-assisted growth of nanostructures and their use as field emission devices, the herein presented general synthesis route for the preparation of low refractive index films on other than bulk substrates—such as on free-standing, ultra-thin membranes—may pave the way for the employment of porSiO2 in micro-electro-mechanical systems.

A Model for Investigating Sources of Li-Ion Battery Electrode Heterogeneity: Part II. Active Material Size, Shape, Orientation, and Stiffness

This work is the extension of our previous paper [Nikpour et al., J. Electrochem. Soc. 168, 060547, (2021)] which introduced the multi-phase smoothed particle (MPSP) model. This model was used to simulate the evolution of the microstructure during the drying and calendering manufacturing processes of four different electrodes. The MPSP model uses particle properties to predict overall film properties such as conductivities and elastic moduli and is validated by multiple experiments. In this work, the model is used to investigate the effects of active material particle size, shape, orientation, and stiffness on graphitic anodes. The model predicts that smaller active particles produce higher calendered film density, electronic conductivity, MacMullin number, and Young’s modulus, as compared to larger active particles. Rod-shaped active materials have greater ionic transport and lower electronic transport compared to the disk and sphere shapes, which have similar transport properties. During calendering, disk-shaped particles tend to be oriented horizontally, which decreases through-plane ionic transport. Increasing the stiffness of the active material increases film porosity and composite Young’s modulus, while lowering electronic transport and increasing ionic transport.